Method for treating heavy hydrocarbon oils



` ct; 2K, T930.' A. A. F. M. sElGLE 1,779,829

. METHOD FOR TREATING HEAVY HYDROCARBON OILS I original Filed Deo. 12, 1925 Patented Oct. 28, 1930 PATENT oFFlcEf ADOLPHE amonia- FRANoIs Manrus sEIGLE. oF rams, ramon METHOD FOR 'IREATING HEAVY HYDROCARBON/OILS Original application led December 12, 1923, Serial No. 680,059,`and in`France Hay 19, 1923. Divided and this application filed August 9, 1927. Serial 110.211,798.

The present invention relates to improvements in the methods and installations described in my pri'or U. S. Patent 1,702,275 and in m'y copending patent application No. 81,144 of January 14, 1926, for treating liquid or liqueiiable hydrocarbons such as crude oils the like. According to these prior methods the hydrocarbons to be treated are vaporized and the vapors thus produced are led at a pressure slightly above or substantially equal to atmospheric pressure, to one or more retorts containing metallic chips or turnings acting to depolymerize thehydrocarbons and in which they are circulated according to a tortuous path, and the superheated gases and vapors discharged by said retorts are then subjected, in groups of cooler expanders, to successive periods of intensive and concomitant expansionand cooling, the cool-v ing fluid used in these apparatus being boiling water.

One characteristic feature of the present invention resides in that the hydrocarbons condensed during each stage ofintensive and concomitant cooling and expansion are returned yto the previous cooling stage. One very material advantage resulting therefrom resides in that the liepiid fuel thereby obtained possesses the characteristic features which are described in my copending application 680,059 of December 12, 1923, of which this application is a division, and which will be hereinafter set forth.

Having thus pointed out the main feature of the method'l according to the invention and the advantages' offered thereby I will now describe the same in detail with reference to the' appended drawing which shows diagrammatically an installation for carrying out the said method, and in which:

Fig. 1 is a general viewand Figs. 2 and 3 are detail-views on a larger scale.

According to the herein 'described process any one of the raw materials above specified,

crude petroleum or shale oils, fuel oils, gas

oils, ete., may be used, 'but in order to facilitate the comprfehensionofthe following process, will be applied to the treatment of crude petroleum, wherefrom the water and the usual gasoline have been preliniinarily eXtracted, -and whose density at 15 C. is 0.897, its ignition point (inan open vessel) being 80 C. If such crudepetroleum is treated b fractional distillation, no vapour is given off7 upto 140 C.; up to 200 0:, 5

per cent is vaporized; up to 300 C., 33 per cent is vaporized; up to'350 C., 85 per cent is vaporized and the residue consists-ofl 15 per cent of dry tar.

`In a vaporization apparatus or boiler u suitably heated by a combustible of .any kind, the oil is introduced in a'continuous manner after having been preliminarily heated to 200 C. in the heater v (Fig. 1); this petroleum is raised in the boiler to its temperature of maximum vaporization i. e. 350 C.,

and the hydrocarbon vapours thus generated are then brought to the bottom of a heatlng Patent No. 1,702,275. l

These vapours enter through the pipe a,`- according-to the arrow 1, and at a pressure substantially equal to the atmosphere pressure, into the bottom of the worm retort A (Fig. 1), circulate upwardly by their natural ascension in the annular art b divided by the discs e (Figs. 1 and 2l), `and during this upward circulation they are caused to iiow through metallic chips or turnings xp laid upon said discs. 1'

This method of circulation' affords a gradualand systematic superheating of the vapours of oil or heavy hydrocarbonsto a determined and easily adjustable -temperature, without risk of an abrupt decomposition, such as takes1 place in ,cracking apparatus; the metallic chips which these vapours are caused to meet with upon the `whole of their path will on the one hand r gulate. the temperature and on the other han will exercise a catalytic action upon these hydrocarbons.

The'metallic fragments used are the waste Aretort'A 'of the type described in my prior from machine work upon pieces of iron,

Aio

ing tube t shall correspond to the temperatures necessary for a suitable catalytic action.

In order to increase the combined effects of heat and catalysis and to ensure an effective stirring of the hydrocarbon molecules, the circulation of the latter `is alternately reversed according to the arrows 2, as shown in Fig. 2.

The hydrocarbon vapours are thus raised in the retort to a temperature between 520 and 530 C., after having been subjected to a molecular transformation due to the action of the catalysts which, as is well known have more or less marked afnities for' carbon and h drogen, and eii'ect at one or another favoura le temperature, a dis lacement of the atoms of one or the other o these two substances, which results in a mixture of rcompounds having physical properties (viscosity, ignition point, density, etc.) which arequite different from those of the original hydrocarbons. In short, hydrocarbons are produced v in which the atomic groups are less and less v thus maintained in ebullition and at a pressure of 10 to 12 'kilogrammes in the annular space between d and d and in the cylindrical body e7 so that a constant temperature be' tween 200.and 220 C. will prevail in the. part wherein the hydrocarbon vapours cirv culate.

Inthisexpansion and cooling apparatus, hydrocarbon vapours aresubjected to two contrary aetions; on the one hand the molecular expansion produced bythe change in the volume occupied by the vapours, and on the other hand the. contraction due to the abrupt cooling.

The hydrocarbon vapours are discharged,

wat the lower part of the expansion and cooling apparatus B, into a space whose diameteris 10 or 15 times that of the orifice leading thereto, and hencethe molecules composing these vapours will widen out, so to speak,

v and will-hence become more voluminous; so

that a molecular expansion is in 'fact produced.

Tco

Moreover these discharged :vapours'are at a temperature of 30 C. and since the water boiling under pressure is maintained in the apparatus between 210 C. 'and 220 C., these 'same hydrocarbon vapours will undergo a ver abrupt cooling,l and their tem erature fa at once from 50 .to' 250 and a molecular-contraction necessarily takes place. These. simultaneous -and contrary, actions result in a great disturbance in the molecules,

and the metallic fragments g disposed on the discs g will facilitate certain molecular rearrangements betweeii the unduly heavy hydrocarbon vapours and the very light roy vapours, or even gases, and which, -when properly associated together, will produce a light fuel analogous to gasoline, thus completing the physico-chemical reactions which commenced in the retort. v

Furthermore, certain light hydrocarbons of an unstable nature, formed inthe retort,

are definitely fixed in the stateof stable combinations'by the expansion and contraction to which they are subjected.

But the -oil has not been entirely decomv posed into lighter hydrocarbons and a part of the same remains in its original state of more or less heavy hydrocarbons; the fraction distilling above 240250 C. is condensed and falls to the bottom of the expansion apparatus whence it is evacuated through a pipe k and returns into the boiler 'v after being mixed, if necessary, with a portion of petroleum not yet treated supplied by a pipe z', and which it will thus heat to a temperature of about 200 C.,in order to prevent sudden vaporization of said fresh petroleum in the boiler.

The hydrocarbons remaining in the state of vapour below 250 C. and composed for the major part, of the above said light prod-l ucts which have just been manufactured, are led (arrows 5) into a second expansion and cooling apparatus C of-a like construction, but wherein the pressure of the boiling water is maintained at only 3 kilogrammes, i; e. at a temperature of about 135 C;

They saine physical and catalytic actions are repeated in said second ap aratus C, but

now onlyupon hydrocarbons distillin -below 250 C. and whereof the major part as already undergone a total transformation or a partial doubling; so that'the catalytic work in this second expansion'and cooling aplparatus is simplified, and a definite stabi ity takes place within the mass of thefhydrocarbons wherein the atoms'of carbon and hydrogen, or their groups of hydrocarbon molecules, were notyet in a perfectly fixedstate.

Those of'- said hydrocarbonswhich distil above 180 C. will condense and fall to the bottom of the second .expansion apparatus C,

'-whence they are evacuated through a'pipe m and are led to the bottom of the first expansion and cooling apparatus B.

The pipem, as shownin the drawing (Fig.

3) opens into the above mentioned pipe h through which the hydrocarbons condensed f in the apparatus B are returned to the boiler '11. But the hdro'carbons discharged from the apparatus C., as above said, while thehydrocarbons are ata temperature of 250o V flowing down through the pipe m and disi charged into the pipe h are at a temperature below 180 C. Hence, since thc-latter hydrocarbons are those whose boiling point is be tween 250 C. and 180 C., when they bc. come mixed with thosedischarged from the a paratus B at a temperature of 250 C., i. e. above `their boiling point, instead of flowing down throughthe pipe h together with the hydrocarbons discharged from B, they-will be once more vaporized and the vapors will ascend and re-enter the lowerl end of the cooler-expanderB. They are therein mixed with the vapours issuing from the retort A, are thus further reheated bythe latter to a higher temperature and are again submitted to the intensive and concomitant cooling and expansion which takes place in B. The valves o1 oz o3 are used for taking olf from time to time a small amount of the various liquids for testing purposes.

The ignition point of the said product is somewhat below that of the usual gasoline extracted from petroleum, while possessing a density greater than that ofthe said gasoline, and a like caloric and thermodynamic efficiency.

Further characteristic features of a purely chemical nature are successively mentioned below; the new product has the same ercentage composition of hydrogen and car on as the non-inflammable and more or less heavy oils, and even viscous oils, from which it was extracted, and which, omitting their percentage of oxygen, sulphur, etc., contain 'as aI rule from 88 to 89 parts by weight of carbon for 12 to 11 parts of hydrogen, whilst the analogous composition of the standard 'this whatever may Vgasoline is from 85 to 86 parts of carbon by weight for 15 to 14 arts of hydrogen, and

e the origin and percentage composition of the crude or heavy petroleums from which the said standard gasoline lhas been extracted. y

In short, the aggregate of light hydrocarbons composing the product according `to the invention is isomeric with the aggregate of the original heavy hydorcarbons, whilst (as is known) the hydrocarbons composing the standard gasoline obtained by cracking or by a mere distillation are, on the whole, the homologues of their original hydrocarbons,

due to the. increase in hydrogen or the diminution in carbon of the percentage composition of the latter. l

Furthermore, the hydrocarbons composing the product 'according. to the invention are mainly unsaturated hydrocarbons, whilst y most of the homo ogous hydrocarbons en tering into the co osition ofthe standard gasolines are saturated hydrocarbons. y A direct consequence of this latter feature isv that the new .product/'is much more sensitive tothe action of certain' chemical agents than the gasolines ofthestandardtype. For

Weight of carbon. for 12.----11` parts o instance the sulphuric acid partially4 converts the new product into sulpho-con]u gated derivatives or various sulphonated products Whose colour variesV from a bright or another reagent.

This fact is all the more characteristic as it is constant, even when the origin of the crude. or heavy petroleum or shale oils used as raw material is changed.

Avfurther difference between the new product and the standard gasolines ,extracted from petroleum resides in that these latter are. as is Well known, insoluble in the ethyl,

methyl or amyl alcohols, unless an auxiliary l or solvent suitable substance, s'uchnas ether, be used. whereas the vnew liquid fuel is directlv very soluble in all said alcohols, and in all proportions, if the alcohols are "absolute. and asfar as 80 to 85 per cent of fuel in the industrial alcohols. "Further, such alcoholic solutions are entirely stable, and remain liquid at 'atemperature of f3`5 C.

The above mentioned characteristics clearly differentiate the jproduct according to the invention'l from 'the other light and iniiam-A mable hydrocarbons obtained from petroleum or shale, which are already known, and

now will .be given the principal characteristic features which diil'erentiate the same from the equally lightand inflammable'hydrocar-A bon extracted from ythe coalpeat or lignite ta'r` and 'which is usually sold underthe denomination of benzol.

1. When treated with nitric acid, ythe `fractional parts of the new product which distil between 80 and 90 C., do not furnishfnitrobenzine, whereas the same fractional parts of benzol will furnishr it in abundance.'

2. The new product in the'crude state vhas a density of .0.735 to 0.780, according to the nature ofthe raw materialffrom which it has been extracted, whilst refined benzol hasv a density of about' 0.870 to 0.890. 3. A somewhat kintensive'c'ooling to 30 or 35 C. has no eect upon the newfproduct, whereas benzol becomes frozen throughout the mass at `4 C. 'y

4. Leaving out of account its small pro-l portion of oxygen, sulphur, etc., the elemen-l tary composition of the new product is, as has been above said, from 88 to 89 parts by hydrogen, whereas the average composition of benzol is 92 parts by Weight of carbon for 8 parts of hydrogen.

j The hydrocarbons which are not condensed in the second expansion and cooling apparatus C proceed according to the arrows 6 intoan ordinary condenser 1' with cold water or air circulation, in which is condensed the new liquid fuel according to the invention, and Whose principal characteristic features have been above explained. Said product is then collected through thel cock or valve lnl in one of the :essels in common use for the storage or transportation of petrols, gasoline or other volatile liquid products.

It is to be noted that the above mentioned maximum temperature of 520-530 C. applies to the treatment of the special oil specified` butmay be widely varied. according to the nature of the raw oil used, and, as a matter of fact, may be comprised between ing industry.

500 and 700 C., as is well known in crack- I-Iaving now described my invention, what `I claim as new' and desire to secure by Let- 4 ters Patent is:

1. Method for the transformation of heavy hydrocarbons comprising a preheating stage for vaporizing the raw hydrocarbon, a main heating stage which consists in'heating, in a very regular and gradual manner, the vapors formed during said preheating stage, the gaseous hydrocarbons produced during said main heating stage being successively submitted to the action of eatalyzers, the maximum temperature vbeing substantially comnumber of successive cooling stages to which the mixture ofga'ses' and vapors issuing from said main heating stage are subjected, the

cooling medium used in the first cooling stage being boiling water at a predetermined vsuperatmospheric pressure so that the sud;

den drop in .the temperature of said gases and vapors through said rst'cooling stage be at least 250 C., the condensate in each cooling stage, from the second stage on, be-

ing Vreheated and revaporized and then again tively their specific action at the temperatures in said cooling stages, the coolin medi- 'um in the first cooling stage being oiling water at a predetermined superatmospheric pressure so that the sudden drop in the temperature of .said gases and vapors throu h said first cooling. stage be at least 250 the condensate in each cooling stage, from the second stage on, being reheated and revaporized and then again submitted to the action of the previous cooling stage and of the corresponding catalyzer.

3. In the method as-claimed in claim 1 the' further feature residing in that the condensate in each cooling stage, from the second stage on, is reheated and revaporized by mixing the same with the hydrocarbon gases and vvapors entering the previous cooling stage.

4. In the method as claimed in claim 1 the further feature residing in that the condensate in each cooling stage, :froml the second stage on, is reheated and revaporized by mixing the'same successively with the condensate in the previous cooling stage and then with the hydrocarbon gases and vapors entering said latter stage.

In testimony whereof I have signed my name to this speciication.

ADOLPHE ANTOINE FRANCOIS MARIUS SElGlLE.

for vaporizing the raw hydrocarbons, a man1 heating stage which consists in heating, in a very regular and gradual manner, the vapors formed during said preheating stage, the gaseous hydrocarbons produced during said main heating stage being successively'submitted to the action-of catalyzers, the maximum temperature being substantially com- -1 prised between 500 C. and 700 C., and a number of successive cooling stages to which the miirture of gases and vapors issuing from said main heating stage are subjected, in the presencef-of other ca'talyzers having respec- 

